CN1195797C - 热塑性弹性组合物 - Google Patents
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Abstract
一种交联或至少部分交联的热塑性弹性组合物由10-90%重量的第一种聚合物和90-10%重量的第二种烯烃聚合物组成，第一种聚合物由乙烯、α-烯烃和视具体情况而定的非共轭二烯组成，其中至少第一或第二种聚合物中的一种至少部分是茂金属聚合反应的产物。
Description
发明领域
本发明涉及至少部分交联的烯烃热塑性弹性体，该弹性体至少含有一种茂金属方法制备的聚合物。
发明背景
烯烃热塑性弹性体已被广泛使用，尤其是作为硫化橡胶的替代品，更尤其是在模塑产品领域。这些交联烯烃热塑性弹性体具有优异的性能，包括拉伸强度、断裂伸长、弹性性能和耐热性。
历史上，上述许多种弹性体是用Ziegler-Natta催化反应制备的聚合物构造的。但是，正如引用在本文中做参考的US5,198,401和WO97/11115中所描述的那样，在离子茂金属催化剂存在下，烯烃、二烯烃和炔属不饱和单体聚合成均聚物和共聚物正制备出独特的材料。例如，通过茂金属催化方法制备的聚丙烯通常至少基本上是全同立构，并且经常是完全全同立构。作为茂金属催化得到的独特化合物的另一个实例是制备低乙烯含量的EPR。具体地说，该反应是在具有下述通式的茂金属催化剂存在下进行的
CpmMRnXq
其中Cp是环戊二烯基环或其衍生物；M是IV、V或VI族过渡金属；R是具有1-20个碳原子的烃基或烃氧基(hydrocarboxyl)；X是卤原子；m＝1-3；n＝0-3；q＝0-3；以及m+n+q的之和等于过渡金属的氧化强度。茂金属催化剂和方法的其它实例公开在US4,530,914、4,871,705、4,937,299、5,124,418、5,017,714、5,120,867、5,278,119、5,304,614、5,324,800、5,347,025、5,350,723、5,391,790以及5,391,789中，其中的每一篇专利文献都引用在本文中做参考。
发明概述
本发明的主要优点是提供具有更优异性能和/或更低的生产费用的新型的和提高了动态硫化性能的热塑性弹性体(TPEs)。
本发明的其他目的和优点将部分在下述说明中给出，而部分将从说明中显而易见或者通过本发明的实施例得到。本发明的目的和优点可以通过后附的权利要求中特别指出的方法和组合实现和得到。
根据本发明的目的，正如本文中实施的和详细描述的那样，本发明的组合物包括交联或至少部分交联的热塑性弹性组合物，该组合物由10-90％的第一种聚合物和90-10％的第二种烯烃聚合物组成，第一种聚合物由乙烯、α-烯烃和视具体情况而定的非共轭二烯组成，其中至少所说的第一种或第二种聚合物中的一种至少部分是茂金属催化聚合反应的产物。在这点上，第一种或第二种聚合物可以由两种或多种聚合物的混合物组成，这些聚合物中至少一种是茂金属聚合物。
在本发明的一个形式中，第一种聚合物是乙烯-丙烯-二烯-聚亚甲基弹性体，即EPDM。正如本文中所使用的，EPDM意欲反映出乙烯、丙烯和非共轭二烯的三元共聚物。在本发明的另一个方式中，共聚物是有时称做EPR有时称做EP(D)M的乙烯和丙烯的弹性体，其中二烯是任意选用的。
在本发明特别优选的形式中，EP(D)M橡胶中乙烯含量小于40％。更优选EP(D)M橡胶中乙烯含量小于20％重量。但是，可以相信，即使C2含量大于40％，茂金属EP(D)M也可以具有某些优点。
适合用于本发明热塑性相中的聚烯烃包括热塑性结晶聚烯烃、均聚物和共聚物。这些聚合物最好是由具有3-6个碳原子的单烯烃单体例如丙烯、1-丁烯、异丁烯、1-戊烯等制成，优选聚丙烯。
在本发明的另一个优选形式中，第二种烯烃聚合物是聚丙烯。在特别优选的形式中，聚丙烯是茂金属衍生的聚丙烯。在另一个实施方案中，向组合物中加入第三种或更多种聚合物。
附图的简单说明
本发明在于表明和描述的新组分、新结构、新排列、新组合和改进。引用并构成说明书一部分的附图同说明书一起说明了本发明的一个实施方案并负责解释本发明的原理。
图1是本发明的TPE配混物在23℃熔体流动速率对韧性对照图；
图2是表示200℃ACR粘度对熔体流动速率对照图；
图3是不同熔体流动速率的Ziegler-Natta聚丙烯对茂金属聚丙烯的应力-应变对照图；
图4是基于20MFR和30MFR的聚丙烯的DVA的螺线流动对照图；
图5是基于0.7和5MFR的聚丙烯的DVA的螺线流动对照图。
本发明的详细说明
现在将对本发明的优选形式详细进行说明。尽管本发明将结合优选实施方案进行说明，但是应该认识到这并不意味着将本发明限制为这些实施方案。相反，本发明意欲包括后附的权利要求中限定的包括在本发明的精神和范围之内的所有变化、改进和等效方式。
本发明具体涉及弹性体相例如茂金属乙烯、α-烯烃(二烯)聚亚甲基橡胶例如乙烯-丙烯(二烯)聚亚甲基橡胶EP(D)M和/或热塑性相例如茂金属聚丙烯。尽管丙烯是代表性弹性体中最通用的α-烯烃，但是也可以使用其他的单体例如1-丁烯、1，4-甲基-1戊烯、1-己烯、辛烯、1-癸烯以及它们的混合物。并且，在具体实施例中，本发明涉及使用EP(D)M橡胶作为动态硫化合金(DVA)组合物的弹性体组分而聚丙烯作为合金的塑性组分，其中的一种组分是茂金属催化方法的产物。
业已发现，动态硫化合金中使用的茂金属EP(D)M使韧性系数至少增加了2。本发明的动态硫化合金包括例如EP(D)M和热塑性结晶聚烯烃的均聚物或共聚物的硫化混合物。事实上，本发明涉及意外的发现，即茂金属催化反应制备的乙烯含量为10-40％重量的EP(D)M聚合物是用于动态硫化合金的优异的弹性体。更尤其是，业已发现，低乙烯含量的EP(D)M聚合物(i)甚至在相对低的门尼粘度下在DVA中也具有特别优异的性能以及(ii)具有更低的粘度对剪切速率的关系。重要地是，C2含量低于40％的EP(D)M同常规EP(D)M相比在DVA中具有等效的或提高了的物理性能，但是费用却更低。目前，作为本发明重点的特殊的EP(D)M是那些通过茂金属催化方法制备的聚合物，该催化方法是制备这些低乙烯含量聚合物的优选方法。并且，通过当今Ziegler-Natta催化剂(Z)制备的EP(D)M不能聚合成低C2含量的聚合物。但是，如下述数据说明的，在DVA中结合使用Ziegler-Natta和茂金属的EP(D)M也得到了改进。
在本发明的优选方式中，可以使用三元共聚物即EPDM。合适的非共轭二烯包括5-亚乙基-2-降冰片烯(ENB)、1，4-己二烯、5-亚甲基-2-降冰片烯(MNB)、1，6-辛二烯、5-甲基-1，4-己二烯、3，7-二甲基-1，6-辛二烯、1，3-环戊二烯、1，4-环己二烯、乙烯基降冰片烯(VNB)、二环戊二烯(DCPD)。
本发明除了涉及通过使用低乙烯含量的EP(D)M提高动态硫化合金的性能之外，还发现，由EP(D)M和热塑性烯烃聚合物/共聚物热塑性材料组成的动态硫化合金的性能当热塑性烯烃聚合物/共聚物通过茂金属催化方法制备时可以显著地提高。优选使用聚丙烯。
更具体地说，为了提高通常用热塑性弹性体的流动定义的DVA的加工性，要求或者降低硫化态或者含有低分子量聚丙烯。另外，提高流动可以通过加入含量相对高的烃油和/或用抗冲击聚丙烯共聚物代替全同立构聚丙烯均聚物来实现。不幸地是，这些方法中的每一种通常都对最终产品的物理性能产生负面影响。
但是，现在业已发现，在形成基于聚丙烯-EP(D)M的DVA中，使用更高熔体流动速率的茂金属聚烯烃，尤其是聚丙烯显著地提高了组合物的溶体流动(或产生了更低的粘度)而并不对配混物的综合物理性能产生明显负面影响。使用Ziegler-Natta聚合的聚丙烯，需要使用部分MFR(高分子量)聚丙烯以产生类似的应力-应变特性。使用茂金属聚丙烯的附加优点是它的结晶温度Tc更高，这一点将降低注塑成型中的循环时间。
用在本发明说明书和后面的权利要求中的术语“聚丙烯”包括丙烯均聚物以及聚丙烯共聚物反应体，该共聚物中可以含有大约1-20％重量的乙烯或4-16个碳原子的α-烯烃共聚单体以及它们的混合物。并且，认为茂金属聚丙烯和Ziegler-Natta聚丙烯结合使用也可以形成性能优异的DVA。
鉴于上述理由，在本发明特别优选的方式中，DVA由热塑性茂金属聚烯烃，特别是聚丙烯和茂金属EP(D)M组成或由这些聚合物与Ziegler-Natta热塑性体和/或弹性体的混合物组成。
本发明的DVA优选高温(例如180℃)下在高剪切设备中橡胶硫化剂存在下通过熔融混合形成。动态硫化的起点伴随有混合扭矩迅速增加以及温度升高。采用动态硫化得到制备的这些DVA的典型形态通常由分散在连续的聚烯烃基体中的大小为0.2-5μm的圆形和不规则形的橡胶颗粒组成。当然，共连续态或共连续相也可能依赖于橡胶(例如EPDM)对塑料(如聚丙烯)的相对量和橡胶的硫化体系或硫化度而转化。
橡胶最好至少是部分交联，可以完全或全部交联。部分或完全交联可以通过下述方法得到：向聚烯烃和弹性体混合物中加入合适的橡胶硫化剂，然后在常规硫化条件下使橡胶硫化到理想的程度。但是，优选通过动态硫化方法交联橡胶。
用于说明书和权利要求中的术语“动态硫化”意思是指对在热塑性弹性体组合物中所含的橡胶的一种硫化方法，其中橡胶是在高于聚烯烃组分熔点的温度下高剪切条件下硫化的。尽管其他形态也可能存在，但是该橡胶同时交联并以细颗粒的形式分散在聚烯烃基体中。
动态硫化可以通过高温下常规的混合设备例如辊炼机、Banbury密炼机、Brabender密炼机、连续密炼机、混合挤出机等中混入热塑性和弹性体组分来实现。该组合物可以通过常规塑料加工技术例如挤出、注塑和压塑成型方法加工和再加工。本领域技术人员可以知道为进行橡胶硫化所需要的合适的硫化剂用量、硫化体系种类和硫化条件。为了得到所需的最佳的交联，该橡胶可以采用改变硫化剂用量、硫化温度和时间来硫化。只要适合特定的烯烃橡胶或使用的橡胶和聚烯烃的混合物的硫化条件，就可以使用任何公知的橡胶硫化体系。这些硫化剂包括含有和不含有硫化促进剂和活性助剂的硫磺、硫给予体、金属氧化物、树脂体系、基于过氧化物的体系、用铂硅烷化或过氧化物等。用于说明书中的术语“完全硫化”和“全部硫化”是指将需要硫化的橡胶组分硫化到某一状态，该状态下交联橡胶的弹性性能同热塑性弹性体组合物之外的橡胶在常规硫化状态下的性能相似。硫化度可以根据凝胶含量或相反地用可提取组分表示。另外，硫化度可以用交联密度表示。
当然，本发明的配混物可以包括其他的硫化剂和增强和非增强的助剂、抗氧化剂、稳定剂、橡胶操作油、增量油、润滑剂、防粘剂、抗静电剂、蜡、起泡剂、颜料、阻燃剂和橡胶配混领域中公知的任何其他的加工助剂。
在本发明特别优选的方式中，正如引用在本文中做参考的US5,290,886中描述的那样，最好是向组合物中加入某些低分子量至中等分子量(小于10,000)的有机酯或烷基乙基醚酯增塑剂。最合适的酯可以包括脂肪族单酯或二酯或另外的低聚脂肪酯或烷基醚酯。为了本发明的目的，特别优选的酯是脂肪族松浆油酸酯/油酸酯例如异辛基松浆油酸酯和正丁基松浆油酸酯。
以橡胶和聚烯烃的重量为基准计，业已发现，制备有用的组合物的热塑性聚烯烃的量通常大约为10-90％重量。热塑性聚烯烃的含量优选大约10-40％重量。
使用下面的通用方法制备本发明的热塑性弹性体，这些方法描述在下表的实施例中。组合物中使用的原料在后面的表中更详细地进行描述。
TPE的制备是在温度不大于180℃高剪切设备中和硫化剂存在下通过熔融混合橡胶、热塑性体和视具体情况而定的稀释剂以使混合和硫化同时进行而制备。其他的添加剂例如填料、稀释剂(油和增塑剂)、抗降解剂等可以视具体情况而加入。
对于本发明的实施例，使用上述方法，其结果在下面表中给出。
表1 Ziegler和茂金属EPDM以及它们的混合物在硬DVA中的实施例
| 实施例# | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| 105B | 0 | 100 | 10 | 20 | 0 | 0 | 0 | 0 | 0 | 0 |
| 105B1 | 0 | 0 | 0 | 0 | 100 | 10 | 20 | 0 | 0 | 0 |
| 96A | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 100 | 10 | 20 |
| V7500 | 100 | 0 | 90 | 80 | 0 | 90 | 80 | 0 | 90 | 80 |
| 51S07A | 219 | 219 | 219 | 219 | 219 | 219 | 219 | 219 | 219 | 219 |
| Sunpar 150油 | 107 | 107 | 107 | 107 | 107 | 107 | 107 | 107 | 107 | 107 |
| SP-1045 | 7 | 7 | 7 | 7 | 7 | 7 | 7 | 7 | 7 | 7 |
| SnCl2 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| 氧化锌 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
| 活性炭黑 | 19.28 | 19.28 | 19.28 | 19.28 | 19.28 | 19.28 | 19.28 | 19.28 | 19.28 | 19.28 |
| EPDM类型 | Ziegler | 茂金属 | 混合 | 混合 | 茂金属 | 混合 | 混合 | 茂金属 | 混合 | 混合 |
| 肖氏D硬度 | 47 | 47 | 48 | 48 | 46 | 47 | 46 | 47 | 46 | 47 |
| 50％应变时的应力，MPa | 10.21 | 10.19 | 10.69 | 10.74 | 9.95 | 10.08 | 10.65 | 9.93 | 10.03 | 10.11 |
| 100％应变时的应力，MPa | 11.31 | 11.21 | 11.82 | 11.68 | 11.04 | 11.20 | 11.90 | 10.52 | 11.23 | 11.32 |
| 200％应变时的应力，MPa | 12.91 | 12.60 | 13.50 | 13.11 | 12.50 | 12.84 | 13.70 | 11.56 | 13.03 | 13.12 |
| 拉伸强度，Mpa | 19.60 | 19.89 | 19.79 | 19.11 | 19.92 | 18.39 | 19.92 | 19.56 | 20.12 | 20.61 |
| 断裂伸长，％ | 461 | 528 | 434 | 442 | 542 | 423 | 428 | 548 | 450 | 466 |
| 韧性，MPa | 63.35 | 73.76 | 61.11 | 60.87 | 75.34 | 56.01 | 61.00 | 72.68 | 62.06 | 65.62 |
| 拉伸变形％ | 35 | 41 | 35 | 36 | 40 | 34 | 35 | 38 | 35 | 35 |
| 重量增加％ | 55.97 | 58.56 | 49.92 | 54.87 | 58.12 | 50.25 | 48.86 | 53.81 | 49.11 | 55.05 |
| 压缩变形％ | 59 | 60 | 61 | 63 | 61 | 57 | 58 | 64 | 57 | 59 |
表2 Ziegler和茂金属EPDM以及它们的混合物在软DVA中的实施例
| 实施例# | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 |
| 105B | 0 | 100 | 10 | 20 | 0 | 0 | 0 | 0 | 0 | 0 |
| 105B1 | 0 | 0 | 0 | 0 | 100 | 10 | 20 | 0 | 0 | 0 |
| RUN96 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 100 | 10 | 20 |
| V7500 | 100 | 0 | 90 | 80 | 0 | 90 | 80 | 0 | 0 | 0 |
| 51S07A | 59 | 59 | 59 | 59 | 59 | 59 | 59 | 59 | 59 | 59 |
| Sunpar 150油 | 107 | 107 | 107 | 107 | 107 | 107 | 107 | 107 | 107 | 107 |
| SP-1045 | 7 | 7 | 7 | 7 | 7 | 7 | 7 | 7 | 7 | 7 |
| SnCl2 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| 氧化锌 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
| 活性炭黑 | 19.28 | 19.28 | 19.28 | 19.28 | 19.28 | 19.28 | 19.28 | 19.28 | 19.28 | 19.28 |
| EPDM类型 | Ziegler | 茂金属 | 混合 | 混合 | 茂金属 | 混合 | 混合 | 茂金属 | 混合 | 混合 |
| 肖氏A硬度 | 73 | 73 | 72 | 73 | 72 | 73 | 73 | 71 | 71 | 72 |
| 50％应变时的应力，MPa | 2.93 | 3.06 | 3.19 | 3.11 | 2.94 | 3.06 | 3.20 | 2.77 | 2.83 | 2.69 |
| 100％应变时的应力，MPa | 4.28 | 4.51 | 4.68 | 4.49 | 4.37 | 4.44 | 4.68 | 4.04 | 4.16 | 3.95 |
| 200％应变时的应力，MPa | 6.65 | 7.25 | 7.49 | 6.99 | 6.92 | 6.98 | 7.30 | 6.28 | 6.69 | 6.34 |
| 拉伸强度，MPa | 11.74 | 9.62 | 8.93 | 9.25 | 11.97 | 9.09 | 8.69 | 10.22 | 8.38 | 8.02 |
| 断裂伸长，％ | 369 | 276 | 250 | 278 | 359 | 279 | 257 | 352 | 260 | 264 |
| 韧性，MPa | 23.51 | 15.19 | 13.23 | 15.03 | 23.38 | 15.06 | 13.63 | 20.19 | 12.68 | 12.27 |
| 拉伸变形％ | 10 | 10 | 10 | 10 | 10 | 8 | 10 | 8 | 8 | 8 |
| 重量增加％ | 79 | 98 | 86 | 95 | 97 | 91 | 91 | 91 | 91 | 95 |
| 压缩变形％ | 30 | 29 | 30 | 33 | 31 | 32 | 34 | 31 | 33 | 32 |
表3 茂金属EPR在DVA中的实施例
| 实施例# | 21 | 22 | 23 | 24 | 25 | 26 | 27 | 28 | 29 | 30 |
| ％ | ％ | ％ | ％ | ％ | ％ | ％ | ％ | ％ | ||
| RG7034 | 100 | 100 | 98.91 | 97.85 | 97.85 | 95.80 | 100 | 97.85 | 95.80 | 95.80 |
| 19397-36A | 0 | 0 | 1.09 | 2.15 | 2.15 | 4.20 | 0 | 0 | 0 | 0 |
| 19397-36B | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 2.15 | 4.20 | 4.20 |
| 100 | 100 | 100 | 100 | 100 | 100 | 100 | 97.85 | 95.80 | 95.80 | |
| phr | phr | phr | phr | phr | phr | phr | phr | phr | phr | |
| RG7034 | 455.74 | 455.74 | 455.74 | 455.74 | 455.74 | 455.74 | 455.74 | 455.74 | 455.74 | 455.74 |
| 19397-36A | 0 | 0 | 5 | 10 | 10 | 20 | 0 | 0 | 0 | 0 |
| 19397-36B | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 10 | 20 | 20 |
| 455.74 | 455.74 | 460.74 | 465.74 | 465.74 | 475.74 | 455.74 | 465.74 | 465.74 | 475.74 | |
| RG7034 | 230 | 230 | 227.50 | 225.06 | 225.06 | 220.33 | 230.00 | 225.06 | 220.33 | 220.33 |
| 19397-36A | 0 | 0 | 2.5 | 4.94 | 4.94 | 9.67 | 0 | 0 | 0 | 0 |
| 19397-36B | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 4.94 | 9.67 | 9.67 |
| 230 | 230 | 230 | 230 | 230 | 230 | 230 | 225.06 | 220.33 | 220.33 | |
| 肖氏硬度D | 43 | 45 | 45 | 44 | 42 | 44 | 43 | 44 | 42 | 44 |
| 100％模量，MPa | 10.31 | 10.39 | 10.44 | 10.02 | 10.88 | 9.90 | 10.31 | 10.07 | 10.21 | 9.87 |
| 拉伸强度，Mpa | 19.2 | 17.33 | 17.71 | 19.32 | 18.85 | 18.56 | 19.2 | 18.34 | 18.23 | 15.85 |
| 断裂伸长，％ | 448 | 389 | 386 | 456 | 418 | 451 | 448 | 441 | 429 | 357 |
| 韧性MPa | 57.6 | 47.92 | 47.58 | 58.22 | 54.7 | 56.41 | 57.6 | 54.84 | 53.81 | 40.73 |
| 拉伸变形％ | 35 | 30 | 33 | 30 | 35？ | 30 | 35 | 35 | 33 | 30 |
| -40℃切口悬臂梁冲击强度 | 699+/-86 | 862+/-82 | 116+/-20 | 828+/-62 | 501+/-99* | 135+/-16 | 699+/-86 | 817+/-53 | 809+/-99 | 112+/-16 |
| NACB | NACB | CB | NACB | ACB | CB | NACB | NACB | NACB | CB | |
| 156+/-41 | 193+/-20 | 808+/-22 | 156+/-41 | 139+/-43 | ||||||
| NACB | CB | |||||||||
| 165CB* |
**样品3，ACB几乎完全断裂 *样品1，完全断裂。
表4 Ziegler和茂金属EPDM在软DVA中的实施例
| 实施例# | 31 | 32 | 33 | 34 | 35 | 36 | 37 | 38 | 39 | 40 | 43 |
| 聚合物类型Ziegler(z)/茂金属(M) | Z | M | M | M | Z | M | M | M | M | M | Z |
| 乙烯，C2％ | 52 | 18 | 17.4 | 17 | 52 | 30 | 31 | 32 | 33 | 40 | 65 |
| ENB％ | 5.7 | 3.1 | 2.85 | 2.5 | 5.7 | 3.2 | 6.7 | 4.2 | 5.8 | 3 | 4.5 |
| V7500，C2＝52％，ML125℃＝91，ENB＝5.7％ | 100 | 100 | |||||||||
| 105B；C2＝18％，ML125℃＝10，ENB＝3.1％ | 100 | ||||||||||
| 105B1；C2＝17.4％，ML125℃＝20，ENB＝2.85％ | 100 | ||||||||||
| 96A；C2＝17％，ML125℃＝100，ENB＝2.5％ | 100 | ||||||||||
| 209B；C2＝30.43％，ML125℃＝30，ENB＝3.16％ | 100 | ||||||||||
| 209C；C2＝31.52％，ML125℃＝37.4，ENB＝6.73％ | 100 | ||||||||||
| 208B；C2＝31.92％，ML125℃＝43.4，ENB＝4.2％ | 100 | ||||||||||
| 208C；C2＝32.88％，ML125℃＝58.2，ENB＝5.8％ | 100 | ||||||||||
| 88B；C2＝40％，ML125℃＝102，ENB＝3％ | 100 | ||||||||||
| VX4779(75phr油)；C2＝65％，ML125℃＝68，ENB＝4.5％ | 175 | ||||||||||
| Rexene 51S07A，0.7MFR PP | 59.10 | 59.10 | 59.10 | 59.10 | 59.10 | 59.10 | 59.10 | 59.10 | 59.10 | 59.10 | 59.10 |
| Sunpar 150 | 107 | 107 | 107 | 107 | 107 | 107 | 107 | 107 | 107 | 107 | 32 |
| SP-1045二水合物 | 7 | 7 | 7 | 7 | 7 | 7 | 7 | 7 | 7 | 7 | 7 |
| SnCl2 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 |
| 氧化锌 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 |
| 活性炭黑 | 19.28 | 19.28 | 19.28 | 19.28 | 19.28 | 19.28 | 19.28 | 19.28 | 19.28 | 19.28 | 19.28 |
| 配方重量 | 295.88 | 295.88 | 295.88 | 295.88 | 295.88 | 295.88 | 295.88 | 295.88 | 295.88 | 295.88 | 295.88 |
| 肖氏A硬度 | 73 | 73 | 72 | 71 | 71 | 66 | 69 | 72 | 71 | 73 | 74 |
| 50％应变时的应力， MPa | 2.93 | 3.06 | 2.94 | 2.77 | 3.37 | 3.07 | 3.13 | 3.22 | 3.13 | 3.18 | 3.81 |
| 200％应变时的应力，MPa | 6.65 | 7.25 | 6.92 | 6.28 | 8.01 | 7.22 | 7.53 | 7.96 | 7.59 | 6.73 | 7.16 |
| 100％应变时的应力，MPa | 4.28 | 4.51 | 4.37 | 4.04 | 4.96 | 4.49 | 4.65 | 4.83 | 4.65 | 4.47 | 5.00 |
| 拉伸强度，MPa | 11.74 | 9.62 | 11.97 | 10.22 | 11.41 | 9.08 | 10.94 | 11.17 | 10.17 | 10.92 | 13.46 |
| 断裂伸长，％ | 369 | 276 | 359 | 352 | 296 | 267 | 298 | 294 | 277 | 353 | 374 |
| 韧性，MPa | 23.51 | 15.19 | 23.38 | 20.19 | 19.12 | 14.31 | 18.17 | 18.58 | 15.95 | 22.00 | 26.92 |
| 拉伸变形％ | 10 | 10 | 10 | 8 | 10 | 13 | 10 | 8 | 10 | 8 | 10 |
| 重量增加％ 125℃下22小时 | 80 | 98 | 98 | 91 | 76 | 100 | 84 | 77 | 85 | 84 | |
| 压缩变形％100℃下24小时 | 30 | 29 | 31 | 31 |
表5 Ziegler和茂金属EPDM在DVA中的实施例
| 实施例# | 44 | 45 | 46 | 47 | 48 | 49 | 50 | 51 | 52 | 53 | 56 |
| 乙烯，C2％ | 52 | 18 | 17.4 | 17 | 52 | 43 | 31 | 32 | 33 | 40 | 65 |
| ENB％ | 5.7 | 3.1 | 2.85 | 2.5 | 5.7 | 3.2 | 6.7 | 4.2 | 5.8 | 3 | 4.5 |
| V7500，C2＝52％，ML125℃＝91，ENB＝5.7％ | 100 | 100 | |||||||||
| 105B；C2＝18％，ML125℃＝10，ENB＝3.1％ | 100 | ||||||||||
| 105B1；C2＝17.4％，ML125℃＝20，ENB＝2.85％ | 100 | ||||||||||
| 96A；C2＝17％，ML125℃＝100，ENB＝2.5％ | 100 | ||||||||||
| 209B；C2＝30.43％，ML125℃＝30，ENB＝3.16％ | 100 | ||||||||||
| 209C；C2＝31.52％，ML125℃＝37.4；ENB＝6.73％ | 100 | ||||||||||
| 208B；C2＝31.92％ ML125℃＝43.4，ENB＝4.2％ | 100 | ||||||||||
| 208C；C2＝32.88％，ML125℃＝58.2，ENB＝5.8％ | 100 | ||||||||||
| 88B；C2＝40％，ML125℃＝102，ENB＝3％ | 100 | ||||||||||
| VX4779(75phr油)C2＝65％，ML125℃＝68，ENB＝4.5％ | 175 | ||||||||||
| Rexene 51S07A，0.7MFR PP | 219.1 | 219.1 | 219.1 | 219.1 | 219.1 | 219.1 | 219.1 | 219.1 | 219.1 | 219.1 | 219.1 |
| Sunpar 150 | 107 | 107 | 107 | 107 | 107 | 107 | 107 | 107 | 107 | 107 | 32 |
| SP-1045 | 7 | 7 | 7 | 7 | 7 | 7 | 7 | 7 | 7 | 7 | 7 |
| SnCl2二水合物 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 |
| 氧化锌 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 |
| 活性炭黑 | 19.28 | 19.28 | 19.28 | 19.28 | 19.28 | 19.28 | 19.28 | 19.28 | 19.28 | 19.28 | 19.28 |
| 配方重量 | 455.88 | 455.88 | 455.88 | 455.88 | 455.88 | 455.88 | 455.88 | 455.88 | 455.88 | 455.88 | 525.38 |
| 肖氏D硬度 | 44 | 45 | 45 | 44 | 43 | 38 | 39 | 40 | 39 | 43 | 45 |
| 50％应变时的应力，Mpa | 9.64 | 9.50 | 9.84 | 9.15 | 10.2 | 9.96 | 10.39 | 9.91 | 9.75 | 9.98 | 10.79 |
| 100％应变时的应力，Mpa | 10.76 | 10.69 | 11 | 10.11 | 11.65 | 11.31 | 11.68 | 11.2 | 11.01 | 10.95 | 11.45 |
| 200％应变时的应力，MPa | 12.47 | 12.72 | 12.84 | 11.79 | 13.81 | 13.50 | 13.75 | 13.18 | 12.91 | 12.48 | 12.92 |
| 拉伸强度，MPa | 20.19 | 17.70 | 22.49 | 20.25 | 23.46 | 17.83 | 21.14 | 19.54 | 19.29 | 22.42 | 22.53 |
| 断裂伸长，％ | 499 | 391 | 495 | 488 | 464 | 364 | 436 | 432 | 449 | 537 | 455 |
| 韧性，MPa | 69.00 | 50.53 | 72.29 | 64.76 | 69.58 | 47.61 | 63.01 | 59.42 | 60.77 | 77.34 | 65.65 |
| 拉伸变形％ | 35 | 40 | 38 | 35 | 35 | 43 | 43 | 35 | 40 | 40 | 43 |
| 重量增加％ | 57 | 62 | 62 | 60 | 53 | 59 | 61 | 53 | 54 | 56 | 52 |
| 压缩变形％ | 57 | 61 | 60 | 61 | 59 | 61 | 60 | 59 | 59 | 65 | 63 |
| -40℃切口冲击强度J/m | 154+/-7 | 24+/-2 | 24+/-2 | 28+/-2 |
表6 Ziegler EPDM和茂金属PP的DVA以及茂金属-Ziegler PP混合物的实施例
| 实施例# | 57 | 58 | 59 | 60 | 61 | 62 | 63 |
| ％ | ％ | ％ | ％ | ％ | ％ | ％ | |
| VISTALON 7500 | 38 | 38 | 38 | 38 | 38 | 0 | 0 |
| 2ZnO/1.5SnCl2的混合物 | 1 | 1 | 1 | 1 | 1 | 0 | 0 |
| SP-1045 | 2 | 2 | 2 | 2 | 2 | 0 | 0 |
| SUNPAR 150M | 40 | 40 | 40 | 40 | 40 | 0 | 0 |
| 51S07A PP Ziegler | 19 | 0 | 2 | 3 | 6 | 100 | 0 |
| 茂金属PP，3MFR | 0 | 19 | 17 | 16 | 13 | 0 | 100 |
| 总量 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| 10min的DSC | |||||||
| 结晶温度，℃ | 94.03 | 89.02 | 94.83 | 95.06 | 95.97 | 106.13 | 98.96 |
| 面积，J/g | 21.54 | 18.28 | 19.11 | 19.84 | 20.35 | 95.23 | 95.36 |
| 熔点，℃ | 154.55 | 138.47 | 140.12 | 142.48 | 145.08 | 166.19 | 152.01 |
| 面积，J/g | 21.18 | 18.57 | 19.00 | 19.20 | 19.93 | 96.38 | 95.55 |
| 肖氏A硬度 | 64 | 63 | 64 | 64 | 64 | ||
| 100％模量，MPa | 2.65 | 2.64 | 2.64 | 2.66 | 2.72 | ||
| 拉伸强度，MPa | 5.70 | 7.02 | 6.95 | 6.26 | 6.81 | ||
| 断裂伸长，％ | 312 | 367 | 353 | 324 | 349 | ||
| 拉伸变形，％ | 9 | 7 | 7 | 7 | 7 | ||
| 压缩变形，％ | 34 | 33 | 31 | 31 | 31 | ||
| 100℃，22h | |||||||
| 125℃24h的重量增加，％ | 131 | 192 | 167 | 152 | 142 | ||
| 重量增加，％ | 134 | 191 | 169 | 156 | 140 |
表7
使用茂金属PP和Ziegler全同立构PP共混物的DVA
| 实施例# | 64 | 65 | 66 | 67 | 68 | 69 | 70 | 71 |
| ％ | ％ | ％ | ％ | ％ | ％ | ％ | ％ | |
| VISTALON 7500 | 38 | 38 | 38 | 38 | 38 | 38 | 38 | 38 |
| 2ZnO/1.5SnCl2的混合物 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| SP-1045 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
| SUNPAR 150M | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 |
| 51S07A PP Ziegler.0.7MFR | 19 | 0 | 2 | 3 | 6 | 13 | 16 | 17 |
| 茂金属PP，3MFR | 0 | 19 | 17 | 16 | 13 | 6 | 3 | 2 |
| 总量 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| 结晶温度，℃ | 103.42 | 91.38 | 92.46 | 99.81 | 96.18 | 108.58 | 99.54 | 100.49 |
| 熔点，℃ | 154.08 | 140.28 | 142.26 | 142.85 | 144.85 | 150.45 | 152.06 | 152.62 |
| 肖氏A硬度 | 64 | 63 | 62 | 63 | 63 | 64 | 64 | 64 |
| 100％模量，MPa | 2.63 | 2.64 | 2.60 | 2.63 | 2.74 | 2.82 | 2.86 | 2.94 |
| 拉伸强度，MPa | 6.75 | 6.46 | 5.72 | 5.95 | 7.53 | 7.33 | 6.77 | 7.41 |
| 断裂伸长，％ | 304 | 286 | 256 | 262 | 307 | 298 | 272 | 286 |
| 压缩变形，％ | 35 | 41 | 37 | 38 | 37 | 33 | 32 | 35 |
| 100℃，22h | ||||||||
| 125℃24h的重量增加，％ | 93 | 113 | 118 | 107 | 107 | 99 | 98 | 96 |
表8 硫化热塑性弹性体(TPE)中茂金属EP(D)M的评价
| 实施例# | 72 | 73 | 74 | 75 | 76 | 77 | 78 |
| V7500 | 100.00 | 90.00 | 80.00 | 60.00 | 90.00 | 80.00 | 60.00 |
| 105B C2＝18％ | 0.00 | 10.00 | 20.00 | 40.00 | 0.00 | 0.00 | 0.00 |
| 105B1，C2＝17.4％ | 0.00 | 0.00 | 0.00 | 0.00 | 10.00 | 20.00 | 40.00 |
| REXENE 51S07A，0.7MFR | 59.10 | 59.10 | 59.10 | 59.10 | 59.10 | 59.10 | 59.10 |
| Sunpar 150 | 80.25 | 80.25 | 80.25 | 80.25 | 80.25 | 80.25 | 80.25 |
| 239.35 | 239.35 | 239.35 | 239.35 | 239.35 | 239.35 | 239.35 | |
| Sunpar 150 | 26.75 | 26.75 | 26.75 | 26.75 | 26.75 | 26.75 | 26.75 |
| SP1045 | 7.00 | 7.00 | 7.00 | 7.00 | 7.00 | 7.00 | 7.00 |
| SnCl2的二水合物 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 |
| 氧化锌 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 |
| 高度硫化 | 356.85 | 356.85 | 356.85 | 356.85 | 356.85 | 356.85 | 356.85 |
| 肖氏A硬度 | 69 | 70 | 69 | 68 | 69 | 70 | 70 |
| 50％应变时的应力，Mpa | 2.67 | 2.71 | 2.74 | 2.85 | 2.74 | 2.90 | 2.87 |
| 100％应变时的应力，Mpa | 4.07 | 4.04 | 4.07 | 4.19 | 4.09 | 4.29 | 4.24 |
| 200％应变时的应力，Mpa | 6.91 | 6.62 | 6.67 | 6.70 | 6.73 | 6.95 | 6.86 |
| 拉伸强度，MPa | 8.78 | 10.21 | 9.32 | 8.34 | 8.39 | 9.81 | 9.26 |
| 断裂伸长，％ | 258 | 315 | 286 | 258 | 256 | 291 | 281 |
| 韧性，MPa | 2.56 | 17.50 | 14.86 | 12.59 | 12.29 | 16.07 | 14.85 |
| 拉伸变形，％ | 8 | 8 | 8 | 10 | 8 | 10 | 10 |
| 油溶胀％ | 87 | 94 | 95 | 93 | 92 | 93 | 99 |
| Sunpar 150 | 26.75 | 26.75 | 26.75 | 26.75 | |||
| SP1045 | 1.5 | 1.50 | 1.50 | 1.50 | |||
| SnCl2的二水合物 | 1.00 | 1.00 | 1.00 | 1.00 | |||
| 氧化锌 | 2.00 | 2.00 | 2.00 | 2.00 | |||
| 低度硫化 | 264.09 | 256.48 | 256.19 | 257.83 | |||
| 肖氏A硬度 | 60 | 61 | 66 | 66 | |||
| 50％应变时的应力，Mpa | 1.90 | 2.04 | 2.17 | 2.53 | |||
| 100％应变时的应力，Mpa | 2.61 | 2.76 | 2.89 | 3.40 | |||
| 200％应变时的应力，Mpa | 3.86 | 3.92 | 4.06 | 4.66 | |||
| 拉伸强度，MPa | 5.08 | 5.65 | 6.29 | 7.29 | |||
| 断裂伸长，％ | 313 | 380 | 421 | 489 | |||
| 韧性，MPa | 10.16 | 13.98 | 17.06 | 24.07 | |||
| 拉伸变形，％ | 10 | 13 | 13 | 15 | |||
| 油溶胀％ | 182 | 178 | 191 | 184 |
表9 DVA中聚丙烯类型的影响
| 实施例# | 79 | 80 | 81 | 82 | 83 | 84 | 85 | 86 | 87 | 88 | 89 | 90 |
| 聚丙烯类型 | Z | Z | Z | Z | Z | Z | Z | Z | M | M | Z | Z |
| MFR，g/10min | 0.7 | 0.7 | 0.7 | 0.7 | 20 | 20 | 5 | 5 | 5.6 | 5.6 | 0.7 | 0.7 |
| 低MFR | 低MFR | 低MFR | 低MFR | 高MFR | 高MFR | 中MFR | 中MFR | 中MFR | 中MFR | 低MFR | 低MFR | |
| 硫化态 | 部分硫化 | 完全硫化 | 完全硫化 | 部分硫化 | 完全硫化 | 完全硫化 | 完全硫化 | 完全硫化 | 完全硫化 | 完全硫化 | 完全硫化 | 过氧化物硫化 |
| 稀释剂 | S150 | S150 | 无油 | 无油 | S150 | 无油 | S150 | 无油 | S150 | 无油 | P100 | S150 |
| 成分 | phr | phr | phr | phr | phr | phr | phr | phr | phr | phr | phr | phr |
| V7500 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 |
| REXENE 51S07A，MFR0.7 | 50.00 | 50.00 | 50.00 | 50.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 50.00 | 50.00 |
| ARISTECH FP200，MFR20 | 0.00 | 0.00 | 0.00 | 0.00 | 50.00 | 50.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| SHELL PP DX5A15H MFR5.0 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 50.00 | 50.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| PP 18897-066-001，MFR5.6 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 50.00 | 50.00 | 0.00 | 0.00 |
| SUNPAR 150M | 107.00 | 107.00 | 0.00 | 0.00 | 107.00 | 0.00 | 107.00 | 0.00 | 107.00 | 0.00 | 0.00 | 0.00 |
| P100 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 107.00 | 0.00 |
| HT-100 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 107.00 |
| SP-1045 | 1.50 | 7.00 | 7.00 | 1.50 | 7.00 | 7.00 | 7.00 | 7.00 | 7.00 | 7.00 | 7.00 | 1.50 |
| SnCl2的二水合物 | 1.00 | 1.50 | 1.50 | 1.00 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.00 |
| 氧化锌 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 |
| VULCUP 40KE | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 2.54 |
| PERKALINK | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 3.30 |
| 总phr | 261.50 | 267.50 | 160.50 | 154.50 | 267.50 | 160.50 | 267.50 | 160.50 | 267.50 | 160.50 | 267.50 | 267.34 |
表9(续)DVA中聚丙烯类型的影响
| 部分硫化 | 完全硫化 | 完全硫化 | 部分硫化 | 完全硫化 | 完全硫化 | 完全硫化 | 完全硫化 | 完全硫化 | 完全硫化 | 完全硫化 | 过氧化物硫化 | |
| std.聚合物 | std.聚合物 | std.聚合物 | std.聚合物 | std.聚合物 | std.聚合物 | SHELL | SHELL | 茂金属PP | 茂金属PP | std.聚合物 | std.聚合物 | |
| 低MFR | 低MFR | 低MFR | 低MFR | 高MFR | 高MFR | 中MFR | 中MFR | 中MFR | 中MFR | 低MFR | 低MFR | |
| 无油 | 无油 | 无油 | 无油 | 无油 | P100 | |||||||
| 肖氏A硬度 | 56 | 63 | 87 | 87 | 65 | 88 | 65 | 86 | 65 | 85 | 62 | 55 |
| 50％应变时的应力，MPa | 1.37 | 2.09 | 6.52 | 6.14 | 2.06 | 6.22 | 2.06 | 5.88 | 2.13 | 5.84 | 1.84 | 1.49 |
| 100％应变时的应力，Mpa | 1.85 | 3.30 | 9.08 | 8.14 | 3.37 | 8.73 | 3.23 | 8.22 | 3.44 | 8.48 | 2.87 | 2.16 |
| 200％应变时的应力，Mpa | 2.67 | 5.79 | 13.75 | 10.76 | - | 13.26 | 5.71 | 12.44 | 6.21 | 13.20 | 4.89 | 3.27 |
| 拉伸强度，Mpa | 2.87 | 6.28 | 16.66 | 11.46 | 6.20 | 20.50 | 5.79 | 23.16 | 7.54 | 16.56 | 5.16 | 4.03 |
| 断裂伸长，％ | 257 | 218 | 250 | 234 | 201 | 294 | 200 | 337 | 240 | 251 | 214 | 290 |
| 韧性，Mpa | 5.21 | 7.67 | 25.32 | 19.39 | 6.94 | 33.69 | 6.84 | 39.21 | 9.64 | 24.05 | 6.40 | 7.51 |
| 拉伸变形，％ | 13 | 6 | 12 | 19 | 5 | 13 | 5 | 12 | 5 | 12 | 5 | 10 |
| 压缩形变％ | 55 | 21 | 24 | 40 | 22 | 26 | 23 | 23 | 22 | 22 | 21 | 35 |
| 100℃下22h | ||||||||||||
| 重量增加％ | 209 | 92 | 153 | 230 | 90 | 131 | 92 | 138 | 83 | 131 | 104 | 203 |
| 125℃下24hIRM903 | ||||||||||||
| ACR粘度，泊 | 1288 | 5301 | * | * | 1676 | * | 1556 | * | 1951 | * | 2157 | 2485 |
表10硫化态和聚丙烯类型对DVA性能的影响
| 实施例# | 91 | 92 | 93 | 94 | 95 | 96 |
| 组分 | ||||||
| VISTALON 7500 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 |
| REXENE 51S07A，MFR＝0.7(Z) | 50.00 | 50.00 | - | - | - | - |
| SHELL PP DX5A15H，MFR＝5(Z) | - | - | 50.00 | - | - | - |
| PP 18897-066-005**MFR＝6.7，(M)(M) | - | - | - | 50.00 | - | - |
| PP 18897-066-006，MFR＝30，(M) | - | - | - | - | 50.00 | - |
| Aristech FP-200F，MDR＝20，(Z) | 50.00 | |||||
| 性能 | ||||||
| ACR粘度，泊 | 1039 | 2299 | 735 | 1366 | 1579 | 1749 |
| 肖氏A硬度 | 65 | 67 | 65 | 64 | 63 | 62 |
| 比重 | 0.882 | 0.884 | 0.884 | 0.883 | 0.883 | 0.884 |
| 50％应变时的应力，MPa | 2.10 | 2.48 | 2.20 | 1.84 | 1.90 | 1.86 |
| 100％应变时的应力，MPa | 2.76 | 3.52 | 3.09 | 2.62 | 2.73 | 2.52 |
| 200％应变时的应力，MPa | 4.06 | 5.93 | 4.98 | 4.13 | 4.42 | 3.81 |
| 拉伸强度，MPa | 6.79 | 9.37 | 7.72 | 7.76 | 6.19 | 4.87 |
| 断裂伸长，％ | 379 | 297 | 302 | 365 | 283 | 271 |
| 韧性，MPa | 15.08 | 14.32 | 12.51 | 14.68 | 9.78 | 8.09 |
| 拉伸变形，％ | 15 | 10 | 10 | 10 | 10 | 10 |
| 重量增加％ | 173.09 | 97.74 | 111.08 | 123.21 | 135.24 | 156.89 |
| 压缩形变％ | 50 | 38 | 38 | 35 | 36 | 45 |
| *通用组分 | ||||||
| SUPAR 150M | 107.00 | 107.00 | 107.00 | 107.00 | 107.00 | 107.00 |
| SP-1045 | 1.50 | 5.00 | 5.00 | 5.00 | 5.00 | 5.00 |
| SnCl2二水合物 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
| 氧化锌 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 |
表11 不同的Ziegler和茂金属聚丙烯的评价
| 母料 | 稀液 | |||||||||||
| 实施例# | 97 | 98 | 99 | 100 | 101 | 102 | 103 | 104 | 105 | 106 | 107 | 108 |
| 对照 | HCPP | Nuc PP均聚物 | HCPP | PP | PP | 对照 | HCPP | PP | PP | PP | PP | |
| 聚丙烯类型 | AES PP | 4720 | 4702G | 19167-002-001 | 18897-066-001 | 18897-006-003 | AES PP | 4722 | 4702G | 19067-002-001 | 18897-066-001 | 18897-066-003 |
| 纯聚丙烯 | ||||||||||||
| 聚合类型 | Ziegler | Ziegler | Ziegler | Ziegler | 茂金属 | 茂金属 | Ziegler | Ziegler | Ziegler | Ziegler | 茂金属 | 茂金属 |
| MFR | 0.7 | 3 | 3 | 80 | 5.6 | 6.7 | 0.7 | 3 | 3 | 80 | 5.6 | 6.7 |
| Tm，℃ | 161 | 162 | 166 | 161 | 158 | 151 | 161 | 162 | 166 | 161 | 158 | 151 |
| ΔHf，J/g | 93 | 100 | 102 | 104 | 97 | 90 | 93 | 100 | 102 | 104 | 97 | 90 |
| Tc，℃ | 111 | 112 | 125 | 116 | 116 | 111 | 111 | 112 | 125 | 116 | 116 | 111 |
| ΔHc，J/g | 95 | 101 | 107 | 104 | 98 | 89 | 95 | 101 | 107 | 104 | 98 | 89 |
| HDT纯聚丙烯，℃ | 91.5+/-5.2 | 104.6+/-0.97 | 133.6+/-1.8 | 107.7+/-0.9 | 116+/-0.85 | 97.45+/-0.65 | 91.5+/-5.2 | 104.6+/-0.97 | 133.6+/-1.8 | 107.7+/-0.9 | 116+/-0.85 | 97.45+/-0.65 |
| 1％割线的弯曲模量，kpsi纯PP | 104801+/-676 | 115292+/-1120 | 186656+/-1755 | 140648+/-620 | 129870+/-7531 | 128204+/-4930 | 104801+/-676 | 115292+/-1120 | 186656+/-1755 | 140648+/-6206 | 129870+/-7531 | 128204+/-4930 |
| 动态硫化合金 | 性能 | |||||||||||
| 1％割线的弯曲模量，kpsi | 24549+/-415 | 25352+/-875 | 25923+/1249 | 26802+/-147 | 28214+/-349 | 27740+/-260 | ||||||
| 1％弯曲模量，kpsi | 27091+/-57 | 27885+/-977 | 28133+/-1351 | 29628+/-65 | 31501+/-463 | 30985+/-643 | ||||||
表11(续) 不同的Ziegler和茂金属聚丙烯的评价
| 热变形温度℃ | 56.5+/-2.8 | 58.3+/-0.8 | 58.0+/-1.4 | 56.1+/-1.1 | 57.4+/-1.0 | 57.1+/-2.0 | ||||||
| 肖氏A/(D)硬度 | 71 | 72 | 72 | 72 | 71 | 71 | 40 | 40 | 40 | 38 | 41 | 40 |
| 50％应变时的应力，Mpa | 2.37 | 2.41 | 2.48 | 2.27 | 2.49 | 2.32 | 8.44 | 8.69 | 8.87 | - | 8.89 | 8.32 |
| 100％应变时的应力，MPa | 3.54 | 3.55 | 3.76 | - | 3.74 | 3.42 | 9.64 | 9.91 | 10.26 | - | 10.05 | 9.43 |
| 200％应变时的应力，Mpa | 5.27 | 5.61 | - | - | 5.91 | 5.4 | 11.42 | 11.63 | 12.13 | - | 11.61 | 11.02 |
| 拉伸强度，MPa | 7 | 6.68 | 5.6 | 3.11 | 8.05 | 7.39 | 15.02 | 13.71 | 13.91 | 7.01 | 14.86 | 17.64 |
| 断裂伸长，％ | 265 | 252 | 180 | 92 | 306 | 292 | 374 | 312 | 297 | 40 | 370 | 482 |
| 韧性，MPa | 10.97 | 10.06 | 6.14 | 1.88 | 14.69 | 12.6 | 41.5 | 33.14 | 32.39 | 2.41 | 41.63 | 57.79 |
| 拉伸变形，％ | 10 | 10 | 10 | 断裂 | 10 | 10 | 33 | 33 | 33 | 断裂 | 30 | 30 |
| 压缩变形％ | 25 | 26 | 24 | 23 | 20 | 22 | 44 | 45 | 54 | 55 | 52 | 50 |
| 100℃下22h | ||||||||||||
| 重量变化％ | 95.4 | 81.5 | 75.8 | 81.8 | 80.2 | 114.6 | 58.6 | 50.7 | 49.2 | 52.5 | 51.1 | 129.3 |
| 3#流体，125℃24h | ||||||||||||
| -40℃切口悬臂梁冲击强度 | 655+/-45 | 199+/-17 | 198+/-11 | 61+/-4 | 309+/-58 | 509+/-8 | ||||||
| me6055 | NACB | CB | CB | CB | NACB | NACB |
HCPP＝高结晶PP(实施例97-102是由100份V7500、107份P100、59份PP和硫化体系(1.26份氯化锡、7份Sp1045、2份氧化锌、19.28份活性碳黑)组成)(除了219份PP之外，实施例103-108与上述相同)
表12 DVA中不同茂金属PP和Ziegler PP的评价(与表11中实施例97-102中的基本配方相同)
| 实施例# | 109 | 110 | 111 | 112 | 113 | 114 | 115 | 116 | 117 | 118 | 119 | 120 | 121 | 122 | 123 | 124 |
| 稀释剂类型 | SUNPAR | SUNPAR | SUNPAR | SUNPAR | SUNPAR | SUNPAR | SUNPAR | SUNPAR | Plasthall100 | Plasthall100 | Plasthall100 | Plasthall100 | Plasthall100 | Plasthall100 | Plasthall100 | Plasthall100 |
| 聚丙烯，Ziegler(Z)或 | 51S07A(Z) | 51S07A(Z) | 51S07A(Z) | 51S07A(Z) | ||||||||||||
| 茂金属(M) | 18897-066-001 | 18897-066-001 | 18897-066-003 | 18897-066-003 | 18897-066-005 | 18897-066-005 | 18897-066-001 | 18897-066-001 | 18897-066-003 | 18897-066-003 | 18897-066-005 | 18897-066-005 | ||||
| 200℃ACR粘度，泊 | 2149 | 1795 | 1662 | 1598 | 996 | 1047 | 1037 | |||||||||
| 肖氏A硬度 | 73 | 74 | 73 | 73 | 72 | 73 | 74 | 73 | 72 | 72 | 73 | 72 | 71 | 71 | 70 | 70 |
| 50％应变时的应力，MPa | 3.03 | 3.55 | 2.93 | 3.06 | 2.87 | 2.82 | 2.99 | 3.02 | 2.84 | 2.66 | 2.59 | 2.56 | 2.42 | 2.45 | 2.43 | 2.42 |
| 100％应变时的应力，MPa | 4.54 | 5.27 | 4.45 | 4.58 | 4.34 | 4.26 | 4.60 | 4.67 | 4.33 | 3.99 | 3.84 | 3.81 | 3.65 | 3.71 | 3.62 | 3.51 |
| 200％应变时的应力，MPa | 7.46 | 8.57 | 7.22 | 7.33 | 7.10 | 6.96 | 7.71 | 7.93 | 7.09 | 6.44 | 6.09 | 6.05 | 5.92 | 6.07 | 5.88 | 5.58 |
| 拉伸强度，MPa | 10.28 | 12.24 | 10.42 | 11.12 | 10.18 | 10.38 | 11.52 | 11.52 | 10.56 | 9.77 | 8.33 | 7.70 | 7.99 | 8.63 | 8.39 | 7.72 |
| 断裂伸长，％ | 289 | 302 | 300 | 314 | 300 | 305 | 298 | 288 | 308 | 321 | 291 | 270 | 282 | 294 | 304 | 293 |
| 韧性，Mpa | 16.84 | 21.10 | 17.47 | 19.35 | 17.10 | 17.41 | 18.40 | 17.68 | 17.92 | 17.51 | 14.04 | 12.19 | 12.78 | 14.13 | 14.49 | 13.00 |
| 拉伸变形，％ | 10 | 10 | 10 | 10 | 13 | 13 | 10 | 10 | 13 | 10 | 10 | 10 | 10 | 10 | 13 | 12 |
| 重量增加％ | 77 | 78 | 75 | 73 | 85 | 83 | 81 | 82 | 95 | 94 | 84 | 89 | 96 | 97 | 103 | 107 |
表12(续)DVA中不同茂金属PP和Ziegler PP的评价(与表11中实施例97-102中的基本配方相同)
| 压缩变形％ | 28 | 26 | 27 | 29 | 29 | 28 | 26 | 25 | 28 | 30 | 28 | 28 | 26 | 26 | 28 | 31 |
| 27 | 25 | 28 | 28 | 30 | 29 | 27 | 25 | 29 | 29 | 29 | 27 | 27 | 26 | 29 | 32 | |
| 219PP | ||||||||||||||||
| -40℃切口悬臂梁冲击强度，J/m | 206+/-13 | 65+/-8 | 104+/-8 | 111+/-6 | 754+/-35 | 445+/-19 | 671+/-26 | 699+/-16 | ||||||||
| 肖氏D硬度 | 45 | 44 | 45 | 45 | 45 | 43 | 44 | 43 | 42 | 42 | 41 | 42 | 41 | 41 | 41 | 41 |
| 50％应变时的应力，MPa | 9.15 | 10.56 | 10.06 | 10.18 | 9.71 | 9.36 | 9.52 | 9.31 | 9.38 | 9.15 | 9.08 | 9.11 | 8.61 | 8.46 | 8.55 | 8.44 |
| 100％应变时的应力，MPa | 10.27 | 12.09 | 11.35 | 11.45 | 11.16 | 10.59 | 10.78 | 10.60 | 10.79 | 10.27 | 10.25 | 10.23 | 9.66 | 9.41 | 9.66 | 9.42 |
| 200％伸长时的应力，MPa | 11.97 | 14.78 | 13.44 | 13.65 | 13.66 | 12.75 | 13.00 | 12.83 | 13.09 | 11.97 | 12.08 | 11.77 | 11.33 | 10.81 | 11.41 | 10.92 |
| 拉伸强度，Mpa | 18.23 | 24.70 | 20.99 | 22.92 | 24.74 | 23.59 | 24.25 | 25.13 | 21.00 | 18.23 | 19.21 | 17.18 | 20.02 | 19.08 | 20.51 | 17.77 |
| 断裂伸长，％ | 439 | 402.4 | 396 | 405 | 411.6 | 433 | 423.6 | 445 | 411.5 | 439 | 419.4 | 420 | 459.6 | 505 | 466.4 | 472 |
| 韧性，MPa | 55.20 | 62.13 | 54.86 | 58.55 | 60.55 | 61.35 | 60.5 | 64.83 | 56.02 | 55.2 | 53.22 | 51.04 | 57.78 | 61.91 | 59.48 | 56.6 |
| 拉伸变形，％ | 29 | 28.5 | 30.5 | 31 | 32.5 | 31 | 32.5 | 31 | 33.5 | 32 | 32.5 | 32 | 34.5 | 33 | 32.5 | 32 |
| 重量增加％ | 48 | 48 | 44 | 46 | 72 | 75 | 73 | 78 | 54 | 57 | 49 | 51 | 85 | 83 | 87 | 87 |
| 压缩变形％ | 54 | 53 | 52 | 51 | 51 | 48 | 51 | 49 | 54 | 54 | 55 | 57 | 57 | 60 | 56 | 59 |
表13 不同硫化态硬DVA中茂金属EPDM的评价
| 实施例# | 125 | 126 | 127 | 128 | 129 | 130 | 131 | 132 | 133 |
| 组分 | phr | phr | phr | phr | phr | phr | phr | phr | phr |
| V7500 | 100 | 90 | 80 | 60 | 90 | 80 | 60 | 0 | 0 |
| 223B，C2＝12.15％ML125＝12.3ENB＝4.00 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 100 | 0 |
| 236A，C2＝13.98％ML125＝12.9ENB＝5.14 | 0 | 10 | 20 | 40 | 0 | 0 | 0 | 0 | 100 |
| 225A C2＝15.7％ML125＝7.2，ENB＝5.3 | 0 | 0 | 0 | 0 | 10 | 20 | 40 | 0 | 0 |
| Rexene 51SO7A | 220 | 220 | 220 | 220 | 220 | 220 | 220 | 220 | 220 |
| Sunpar 150 | 80.25 | 80.25 | 80.25 | 80.25 | 80.25 | 80.25 | 80.25 | 80.25 | 80.25 |
| 母炼胶配方重量 | 400.25 | 400.25 | 400.25 | 400.25 | 400.25 | 400.25 | 400.25 | 400.25 | 400.25 |
| Sunpar 150 | 26.75 | 26.75 | 26.75 | 26.75 | 26.75 | 26.75 | 26.75 | 26.75 | 26.75 |
| 氧化锌 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 |
| SP1045 | |||||||||
| DVA#1 | 7.00 | 7.00 | 7.00 | 7.00 | 7.00 | 7.00 | 7.00 | 7.00 | 7.00 |
| DVA#2 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 |
| DVA#3 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 |
| SnCl2的二水合物 | |||||||||
| DVA#1 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 |
| DVA#2 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
| DVA#3 | 1.25 | 1.25 | 1.25 | 1.25 | 1.25 | 1.25 | 1.25 | 1.25 | 1.25 |
| 肖氏D硬度 | |||||||||
| DVA#1 | 47 | 47 | 48 | 48 | 47 | 47 | 46 | 48 | 48 |
| DVA#2 | 41 | 43 | 42 | 42 | 42 | 42 | 42 | 44 | 41 |
| DVA#3 | 43 | 44 | 44 | 45 | 44 | 43 | 43 | 45 | 44 |
| 100％应变时的应力，MPa |
表(续)13 不同硫化态硬DVA中茂金属EPDM的评价
| DVA#1 | 10.66 | 10.62 | 1085 | 10.73 | 10.75 | 10.50 | 10.57 | 10.51 | 10.25 |
| DVA#2 | 9.18 | 9.34 | 9.58 | 9.81 | 9.52 | 9.49 | 9.84 | 9.89 | 10.12 |
| DVA#3 | 10.02 | 10.17 | 10.10 | 10.17 | 10.10 | 10.01 | 10.04 | 10.34 | 9.71 |
| 拉伸强度，MPa | |||||||||
| DVA#1 | 21.83 | 21.25 | 20.07 | 19.76 | 21.39 | 20.49 | 18.95 | 17.09 | 18.72 |
| DVA#2 | 13.13 | 13.93 | 13.43 | 14.77 | 14.42 | 14.76 | 14.97 | 15.67 | 16.78 |
| DVA#3 | 18.43 | 19.10 | 18.23 | 18.16 | 18.59 | 18.37 | 17.50 | 18.35 | 17.41 |
| 断裂伸长，％ | |||||||||
| DVA#1 | 476 | 472 | 446 | 462 | 469 | 484 | 452 | 468 | 494 |
| DVA#2 | 454 | 511 | 455 | 551 | 526 | 560 | 592 | 614 | 629 |
| DVA#3 | 499 | 537 | 529 | 534 | 534 | 550 | 539 | 633 | 639 |
| 韧性，Mpa | |||||||||
| DVA#1 | 65.51 | 64.18 | 60.28 | 61.40 | 64.41 | 64.41 | 58.51 | 58.74 | 63.00 |
| DVA#2 | 47.23 | 55.24 | 49.33 | 63.15 | 58.43 | 62.39 | 67.79 | 73.29 | 76.71 |
| DVA#3 | 62.51 | 69.23 | 67.41 | 67.70 | 68.41 | 68.93 | 66.72 | 83.31 | 80.07 |
| 拉伸变形，％ | |||||||||
| DVA#1 | 33 | 33 | 34 | 35 | 33 | 34 | 36 | 42 | 38 |
| DVA#2 | 39 | 39 | 39 | 43 | 41 | 41 | 45 | 47 | 45 |
| DVA#3 | 32 | 33 | 33 | 34 | 33 | 33 | 35 | 41 | 38 |
| 125℃24h重量增加％ | |||||||||
| DVA#1 | 56 | 56 | 55 | 56 | 55 | 56 | 58 | 63 | 59 |
| DVA#2 | 83 | 81 | 82 | 78 | 83 | 82 | 86 | 78 | 79 |
| DVA#3 | 61 | 60 | 60 | 60 | 63 | 62 | 62 | 68 | 66 |
| 100℃22h压缩变形％ | |||||||||
| DVA#1 | 57 | 55 | 54 | 58 | 55 | 58 | 60 | 61 | 57 |
| DVA#2 | 70 | 69 | 71 | 70 | 70 | 74 | 74 | 73 | 75 |
| DVA#3 | 57 | 54 | 57 | 60 | 59 | 61 | 60 | 62 | 64 |
表14 不同硫化态软的DVA中茂金属EPDM的实施例
| 实施例# | 134 | 135 | 136 | 137 | 138 | 139 | 140 | 141 | 142 | 143 |
| 组分 | phr | phr | phr | phr | phr | phr | phr | |||
| V7500 | 100 | 90 | 80 | 60 | 90 | 80 | 60 | 0 | 0 | 0 |
| 223B C2＝12.15％ | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 100 | 0 | 0 |
| 236A，C2＝13.98％ | 0 | 10 | 20 | 40 | 0 | 0 | 0 | 0 | 100 | 0 |
| 225A C2＝15.7％ML125＝7.2ENB＝5.3 | 0 | 0 | 0 | 0 | 10 | 20 | 40 | 0 | 0 | 100 |
| Rexene 51SO7A | 59.1 | 59.1 | 59.1 | 59.1 | 59.1 | 59.1 | 59.1 | 59.1 | 59.1 | 59.1 |
| Sunpar 150 | 80.3 | 80.3 | 80.3 | 80.3 | 80.3 | 80.3 | 80.3 | 80.3 | 80.3 | 80.3 |
| 母炼胶配方重量 | 2395 | 2395 | 2395 | 2395 | 2395 | 2395 | 2395 | 2395 | 2395 | 2395 |
| Sunpar 150 | 26.8 | 26.8 | 26.8 | 26.8 | 26.8 | 26.8 | 26.8 | 26.8 | 26.8 | 26.8 |
| 氧化锌 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 |
| SP1045 | ||||||||||
| DVA#1 | 7.00 | 7.00 | 7.00 | 7.00 | 7.00 | 7.00 | 7.00 | 7.00 | 7.00 | 7.00 |
| DVA#2 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 |
| DVA#3 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 |
| SnCl2的二水合物 | ||||||||||
| DVA#1 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 |
| DVA#2 | 1.10 | 1.10 | 1.10 | 1.10 | 1.10 | 1.10 | 1.10 | 1.10 | 1.10 | 1.10 |
| DVA#3 | 1.25 | 1.25 | 1.25 | 1.25 | 1.25 | 1.25 | 1.25 | 1.25 | 1.25 | 1.25 |
| 肖氏A硬度 | ||||||||||
| DVA#1 | 67 | 69 | 69 | 72 | 71 | 72 | 73 | 67 | 67 | 64 |
| DVA#2 | 65 | 66 | 68 | 69 | 68 | 68 | 69 | 63 | 68 | 64 |
| DVA#3 | 69 | 69 | 69 | 68 | 68 | 67 | 68 | 67 | 68 | 65 |
| 100％应变时的应力，Mpa | ||||||||||
| DVA#1 | 3.71 | 3.75 | 4.01 | 3.99 | 3.92 | 3.86 | 3.91 | 3.72 | 3.65 | 3.25 |
表14(续) 不同硫化态软的DVA中茂金属EPDM的实施例
| DVA#2 | 2.66 | 2.78 | 2.80 | 3.06 | 2.94 | 2.77 | 2.94 | 2.74 | 3.51 | 2.63 |
| DVA#3 | 3.70 | 3.83 | 4.07 | 3.87 | 3.40 | 3.57 | 3.47 | 3.34 | 3.10 | 2.78 |
| 拉伸强度，MPa | ||||||||||
| DVA#1 | 9.30 | 7.52 | 8.61 | 9.04 | 9.08 | 9.45 | 8.40 | 9.44 | 9.08 | 8.11 |
| DVA#2 | 5.50 | 6.14 | 6.38 | 6.95 | 6.29 | 6.07 | 5.69 | 6.45 | 7.93 | 4.87 |
| DVA#3 | 8.20 | 8.03 | 7.82 | 8.45 | 8.38 | 8.44 | 7.39 | 9.95 | 7.91 | 8.18 |
| 断裂伸长，％ | ||||||||||
| DVA#1 | 301 | 250 | 269 | 306 | 305 | 324 | 287 | 345 | 312 | 344 |
| DVA#2 | 334 | 389 | 421 | 451 | 416 | 450 | 461 | 465 | 477 | 407 |
| DVA#3 | 286 | 277 | 260 | 310 | 345 | 346 | 339 | 465 | 365 | 488 |
| 韧性，Mpa | ||||||||||
| DVA#1 | 15.02 | 10.73 | 13.08 | 16.17 | 16.02 | 17.08 | 13.88 | 18.23 | 15.52 | 15.72 |
| DVA#2 | 11.62 | 15.00 | 17.14 | 19.95 | 17.27 | 17.69 | 18.49 | 18.70 | 24.26 | 13.60 |
| DVA#3 | 13.30 | 12.88 | 12.10 | 15.39 | 16.45 | 16.98 | 15.45 | 25.96 | 16.37 | 22.79 |
| 拉伸变形，％ | ||||||||||
| DVA#1 | 8 | 8 | 8 | 8 | 8 | 8 | 10 | 15 | 10 | 13 |
| DVA#2 | 10 | 13 | 15 | 15 | 13 | 15 | 18 | 23 | 20 | 20 |
| DVA#3 | 8 | 8 | 8 | 8 | 8 | 8 | 10 | 18 | 13 | 15 |
| 125℃24h重量增加％ | ||||||||||
| DVA#1 | 89.7 | 90.3 | 93.0 | 92.8 | 92.2 | 96.8 | 103.3 | 130.6 | 108.9 | 128.9 |
| DVA#2 | 228.7 | 185.1 | 184.3 | 188.6 | 200.8 | 187.3 | 200.8 | 193.9 | 207.5 | 218.6 |
| DVA#3 | 103.0 | 104.5 | 101.3 | 106.5 | 117.3 | 113.5 | 116.9 | 166.7 | 139.8 | 168.1 |
| 100℃22h压缩变形％ | ||||||||||
| DVA#1 | 21 | 23 | 25 | 28 | 25 | 26 | 28 | 32 | 32 | 33 |
| DVA#2 | 37 | 35 | 36 | 38 | 41 | 42 | 45 | 52 | 47 | 59 |
| DVA#3 | 22 | 23 | 20 | 24 | 28 | 31 | 28 | 37 | 33 | 37 |
表15 EPDM中使用茂金属/Ziegler聚丙烯的不同硫化体系的实施例
| 实施例# | 144 | 145 | 146 | 147 | 148 | 149 | 150 | 151 | 152 | 153 | 154 | 155 | 156 | 157 | 158 |
| 硫化体系 | R | R | R | R | R | HS | HS | P | P | P | HS | HS | P | P | P |
| 成分 | phr | phr | phr | phr | phr | phr | phr | phr | phr | phr | phr | phr | phr | phr | phr |
| Ziegler V7500 | 100 | 100 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 100 | 100 | 100 | 100 | 100 |
| 茂金属258C，C2＝55.5，ML125℃＝52.1，ENB＝5.86 | 0 | 0 | 100 | 100 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| 茂金属254B，C2＝73.03，ML125℃＝39.5 ENB＝4.92 | 0 | 0 | 0 | 0 | 100 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| Ziegler MDV96-8，VNB EPDM | 0 | 0 | 0 | 0 | 0 | 200 | 200 | 200 | 200 | 200 | 0 | 0 | 0 | 0 | 0 |
| Ziegler Lyondel 51S07A，MFR0.7 | 59 | 0 | 59 | 0 | 59 | 59 | 0 | 59 | 0 | 0 | 59 | 0 | 59 | 0 | 59 |
| 茂金属18897-066-001 | 0 | 59 | 0 | 59 | 0 | 0 | 59 | 0 | 59 | 59 | 0 | 59 | 0 | 59 | 0 |
| Sunpar 150M油 | 107 | 107 | 107 | 107 | 107 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| 氧化锌 | 2 | 2 | 2 | 2 | 2 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| SnCl2 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| SP1045 | 6 | 6 | 6 | 6 | 6 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| HT-100白油 | 0 | 0 | 0 | 0 | 0 | 7 | 7 | 7 | 7 | 7 | 107 | 107 | 107 | 107 | 107 |
| 硅烷 | 0 | 0 | 0 | 0 | 0 | 2.25 | 2.25 | 0 | 0 | 0 | 2.25 | 2.25 | 0 | 0 | 0 |
| PC085，铂催化剂，对VNB EPDM0.75ppm铂；对ENB EP 12ppm铂 | 0 | 0 | 0 | 0 | 0 | 3 | 3 | 0 | 0 | 0 | 3 | 3 | 0 | 0 | 0 |
| Luperox 101XIA5(Luperco 101XL)45％ | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 1.13 | 1.13 | 0 | 0 | 0 | 1.13 | 1.13 | 0 |
| Luperox HP101XLP(Luperco101SL-SR) 44％ | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 1.15 | 0 | 0 | 0 | 0 | 1.15 |
| TAC50％活性 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 3.3 | 3.3 | 3.3 | 0 | 0 | 3.3 | 3.3 | 3.3 |
| 275.5 | 275.5 | 275.5 | 275.5 | 275.5 | 271.3 | 271.3 | 270.4 | 270.4 | 270. 5 | 271.3 | 271. 3 | 270.4 | 270.4 | 270.5 | |
| 肖氏A硬度 | 69 | 68 | 69 | 67 | 72 | 70 | 70 | 66 | 68 | 65 | 64 | 63 | 63 | 68 | 63 |
| 100％应变时的应力，Mpa | 3.70 | 3.43 | 3.67 | 3.34 | 3.65 | 3.71 | 3.47 | 2.83 | 3.34 | 2.75 | 2.93 | 2.87 | 2.45 | 2.93 | 2.21 |
| 拉伸强度，Mpa | 9.59 | 7.81 | 9.14 | 8.46 | 10.71 | 9.25 | 7.99 | 5.58 | 5.51 | 4.66 | 5.08 | 5.28 | 4.75 | 5.07 | 4.11 |
| 断裂伸长，％ | 318 | 287 | 303 | 313 | 414 | 444 | 490 | 355 | 281 | 304 | 339 | 360 | 355 | 302 | 324 |
| 韧性，MPa | 16.48 | 12.52 | 14.99 | 14.37 | 23.64 | 25.05 | 25.26 | 13.21 | 10.60 | 9.72 | 11.90 | 13.09 | 11.18 | 10.33 | 8.72 |
| 拉伸变形，％ | 7.5 | 7 | 7 | 7 | 13 | 12 | 13 | 12 | 15 | 17 | 22 | 20 | 14 | 15 | 15 |
| 125℃24h的重量增加％ | 93 | 90 | 94 | 89 | 111 | 126 | 140 | 171 | 164 | 199 | 201 | 176 | 184 | 177 | 215 |
| 100℃22h的压缩变形％ | 25 | 27 | 23 | 27 | 34 | 38 | 36 | 33 | 45 | 45 | 38 | 39 | 39 | 45 |
尽管根据专利法给出本发明最好的模式和优选的实施方式，但是本发明的范围并不仅限于此，而是通过后面的权利要求进行了限定。
下面给出实施例中的原料及其来源。
原料明细表
Vistalon7500，C2％＝56％，ML(1+4)125℃＝82，ENB＝5.7％，Ziegler催化剂，(Exxon化学公司制造)
Epsyn P597橡胶，用100份石蜡油增量，Ziegler催化剂，(Copolymer Rubber & Chemical Co.-DSM)
VX4779 EP(D)M，C2＝64％，用75份油增量，Ziegler催化剂，(Exxon化学公司制造)
聚丙烯，Ziegler PP，Rexene/Lyondel 51SO7A，0.7MFR，(Lyondel公司)
聚丙烯，Ziegler PP，Aristech FP200F，20MFR，(Aristech公司)
聚丙烯，Ziegler-Natta PP，DX5A15H，(Shell公司)
PP18897-066-001，6MFR，用无载体茂金属催化剂制备的茂金属PP，(Exxon化学公司制造)
PP18897-066-005，6.7MFR，用载体茂金属催化剂制备的茂金属PP，(Exxon化学公司制造)
PP18897-066-006，32MFR，用载体茂金属催化剂制备的茂金属PP，(Exxon化学公司制造)
Sunpar150，(Sun化学公司)
HT-100白石蜡油，Petro Canada
SP-1045，(Schenectady国际公司)
Plasthall100，(C.P.Hall)
Vulkup 40KE，(Hercules)
异氰尿酸三烯丙酯/Perkalink，(Cytec/Akzo)
Lurerox IUIXL(Alf Altochem)
氯化亚锡，(Masson Metals)
硅烷(Dow Corning)
Santoprene 103-40(Advanced Elastomer Systems，L.P.)
RG7034(Advanced Elastomer Systems，L.P.公司)
茂金属聚合物的物理特性
| 聚 合 物EPM/EPDM | Mn×10-3 | Mw×10-3 | MWD | C2 | 门尼粘度ML125℃ | ENB％ | 催化剂* |
| 19397-36A | 80 | 149 | 1.83 | 12 | 2或3 | 0 | 全同立构 |
| 19397-36B | 78 | 142 | 1.82 | 18 | 2或3 | 0 | 全同立构 |
| 19397-52A | 91 | 170 | 1.88 | 15 | 24.8 | 0 | 全同立构 |
| 19397-63B | 163 | 426 | 2.62 | 14 | 95 | 0 | 无规立构 |
| 223B | 98.9 | 177.4 | - | 12.15 | 12.3 | 3.0 | 全同立构 |
| 236A | 107.1 | 187 | - | 13.98 | 12.9 | 4.0 | 全同立构 |
| 225A | 91.9 | 166.3 | - | 15.67 | 7.2 | 5.1 | 全同立构 |
| 105B | 92 | 171 | 1.87 | 18 | 10 | 3.1 | 全同立构 |
| 105B1 | 82 | 161 | 1.95 | 17.4 | 20 | 2.85 | 全同立构 |
| 96A | - | - | - | 17 | 100 | 2.57 | 无规立构 |
| 209B | 98 | 197 | 2.01 | 30.4 | 30 | 3.2 | 全同立构 |
| 209C | 110 | 217 | 1.98 | 31.5 | 37 | 6.7 | 全同立构 |
| 208B | 93 | 192 | 2.07 | 31.9 | 43.4 | 4.2 | 全同立构 |
| 208C | 103 | 206 | 1.99 | 32.9 | 58.2 | 5.8 | 全同立构 |
| 88B | 201 | 452 | 2.24 | 40 | 102 | 3.0 | 全同立构 |
| 258C | - | - | - | 55.5 | 52.1 | 5.86 | 全同立构 |
| 254B | - | - | - | 73.03 | 39.5 | 4.92 | 全同立构 |
聚丙烯物理特性
| 聚丙烯 | MFRg/10min | 二甲苯可溶物％ | 立构缺陷(/10,000mers) | Regio缺陷(/10,000mers) | Mn | Mw | Mw/Mn |
| 18897-066-001 | 6 | 0.21 | 17.5 | 40.5 | 128,302 | 237,362 | 1.85 |
| 18897-066-003 | 6.7 | 2.17 | 22 | 94.8 | 111,201 | 216,170 | 1.94 |
| 18897-066-005 | 6.7 | 2.17 | 22 | 94.8 | 111,201 | 216,170 | 1.94 |
| 18897-066-006 | 32 | 0.24 | 23.3 | 41.7 | 83,732 | 149,876 | 1.79 |
| 51S07A | 0.7 | 3.15 | 84 | 119 | 119,103 | 588,145 | 4.93 |
因此，本发明很明显已经得到了完全满足上面提出的目的和优点的热塑性弹性组合物。尽管本发明结合了本文中的具体实施方式进行了描述，但是显然，根据上面的描述，很多变化形式对本领域技术人员是显而易见的。因此，本发明应包括在后附权利要求精神和宽范围之内的所有这样的变化形式、改进和改变。
Claims (10)
1.一种热塑性弹性组合物由a.10-90％重量选自乙烯和α-烯烃共聚物或乙烯、α-烯烃和非共轭二烯的三元共聚物的至少部分交联的第一种弹性聚合物和b.90-10％重量的第二种热塑性C3-6烯烃聚合物组成，其中至少所说的第一种或第二种聚合物中的一种至少部分是茂金属催化方法制备的产物。
2.权利要求1的组合物，其中所说的第一种聚合物是由茂金属催化方法制备的乙烯-丙烯-二烯三元共聚物和Ziegler-Natta催化方法制备的乙烯-丙烯-二烯三元共聚物的混合物组成。
3.权利要求1的组合物，其中所说的第一种聚合物是乙烯含量小于40％重量的由茂金属催化方法制备的乙烯-丙烯-二烯三元共聚物。
4.权利要求3的组合物，其中所说的第一种聚合物中含有小于20％重量的乙烯。
5.权利要求1的组合物，其中所说的第二种聚合物是聚丙烯。
6.权利要求5的组合物，其中所说的聚丙烯是一种茂金属催化方法制备的产物。
7.权利要求1的组合物，其中所说的第二种聚合物是一种茂金属催化方法制备的产物。
8.权利要求1的组合物，其中所说的第一种聚合物是乙烯、丙烯和非共轭二烯的三元共聚物。
9.权利要求8的组合物，其中所说的非共轭二烯选自5-亚乙基-2-降冰片烯、1，4-己二烯、5-亚甲基-2-降冰片烯、1，6-辛二烯、5-甲基-1，4-己二烯、3，7-二甲基-1，6-辛二烯、1，3-环戊二烯、1，4-环己二烯和二环戊二烯。
10.权利要求1的组合物，其中所说的第一种聚合物是动态硫化的。
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1997
- 1997-12-16 EP EP97952488A patent/EP0946640B1/en not_active Expired - Lifetime
- 1997-12-16 AU AU55286/98A patent/AU731184B2/en not_active Ceased
- 1997-12-16 AU AU56081/98A patent/AU731537B2/en not_active Ceased
- 1997-12-16 KR KR10-1999-7005357A patent/KR100491237B1/ko not_active IP Right Cessation
- 1997-12-16 CN CN97180692A patent/CN1244208A/zh active Pending
- 1997-12-16 TW TW086118974A patent/TW479064B/zh not_active IP Right Cessation
- 1997-12-16 JP JP52794098A patent/JP2002501555A/ja active Pending
- 1997-12-16 IL IL13034697A patent/IL130346A0/xx not_active IP Right Cessation
- 1997-12-16 BR BR9713748A patent/BR9713748A/pt not_active Application Discontinuation
- 1997-12-16 WO PCT/US1997/023189 patent/WO1998027155A1/en not_active Application Discontinuation
- 1997-12-16 IL IL13010497A patent/IL130104A0/xx unknown
- 1997-12-16 BR BR9714409-6A patent/BR9714409A/pt not_active Application Discontinuation
- 1997-12-16 KR KR1019990705359A patent/KR20000057589A/ko not_active Application Discontinuation
- 1997-12-16 DE DE69710778T patent/DE69710778T2/de not_active Expired - Fee Related
- 1997-12-16 CA CA002274531A patent/CA2274531A1/en not_active Abandoned
- 1997-12-16 CN CNB971806993A patent/CN1195797C/zh not_active Expired - Fee Related
- 1997-12-16 CA CA002273794A patent/CA2273794A1/en not_active Abandoned
- 1997-12-16 ES ES97952488T patent/ES2173510T3/es not_active Expired - Lifetime
- 1997-12-16 EP EP97951719A patent/EP0946641A1/en not_active Withdrawn
- 1997-12-16 US US08/991,382 patent/US6268438B1/en not_active Expired - Fee Related
- 1997-12-16 WO PCT/US1997/023273 patent/WO1998027154A1/en active IP Right Grant
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109462990A (zh) * | 2016-05-31 | 2019-03-12 | 陶氏环球技术有限责任公司 | 包括嵌段复合物作为增容剂的热塑性聚烯烃共混物 |
| CN109462990B (zh) * | 2016-05-31 | 2022-05-13 | 陶氏环球技术有限责任公司 | 包括嵌段复合物作为增容剂的热塑性聚烯烃共混物 |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2273794A1 (en) | 1998-06-25 |
| CN1244208A (zh) | 2000-02-09 |
| KR100491237B1 (ko) | 2005-05-25 |
| MY114053A (en) | 2002-07-31 |
| AU731537B2 (en) | 2001-03-29 |
| AU731184B2 (en) | 2001-03-29 |
| AU5608198A (en) | 1998-07-15 |
| KR20000057588A (ko) | 2000-09-25 |
| BR9713748A (pt) | 2000-03-21 |
| EP0946640B1 (en) | 2002-02-27 |
| IL130104A0 (en) | 2000-06-01 |
| JP2001524139A (ja) | 2001-11-27 |
| JP2002501555A (ja) | 2002-01-15 |
| WO1998027154A1 (en) | 1998-06-25 |
| DE69710778T2 (de) | 2002-08-22 |
| ES2173510T3 (es) | 2002-10-16 |
| DE69710778D1 (de) | 2002-04-04 |
| EP0946641A1 (en) | 1999-10-06 |
| AU5528698A (en) | 1998-07-15 |
| EP0946640A1 (en) | 1999-10-06 |
| CN1251603A (zh) | 2000-04-26 |
| US6268438B1 (en) | 2001-07-31 |
| CA2274531A1 (en) | 1998-06-25 |
| TW479064B (en) | 2002-03-11 |
| BR9714409A (pt) | 2000-04-18 |
| IL130346A0 (en) | 2000-06-01 |
| WO1998027155A1 (en) | 1998-06-25 |
| KR20000057589A (ko) | 2000-09-25 |
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